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Issue 48, 2014
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1,2,4,5-Benzenetetrasulfonic acid and 1,4-benzenedisulfonic acid as sulfo analogues of pyromellitic and terephthalic acids for building coordination polymers of manganese

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Abstract

The new polysulfonic acids H4B4S (1,2,4,5-benzenetetrasulfonic acid) and H2BDS (1,4-benzenedisulfonic acid) were used for the preparation of five manganese coordination polymers. The reactions of H4B4S and MnCO3 were performed in dimethylformamide (DMF) or N-methylpyrrolidone (NMP) as solvent in sealed glass ampoules at elevated temperatures. Two benzenetetrasulfonates could be obtained, [NH2(CH3)2]2{Mn(B4S)(DMF)2} (I) (P21/c, Z = 2, a = 942.02(5) pm, b = 1684.86(6) pm, c = 918.45(5) pm, β = 97.746(6)°, R1; wR2 (Io > 2σ(Io)) = 0.0357; 0.0771) and [HNMP]2{Mn(B4S)(NMP)2} (II) (P21/c, Z = 2, a = 931.7(1) pm, b = 1049.2(1) pm, c = 1944.9(1) pm, β = 113.529(3)°, R1; wR2 (Io > 2σ(Io)) = 0.0470; 0.0952). Both compounds exhibit anionic chains according to 1{Mn(B4S)2/2(L)2}2− (L = DMF, NMP). The Mn2+ ions are in octahedral coordination of oxygen atoms. The charge of the anionic chains is either compensated by dimethylammonium cations, [NH2(CH3)2+], or by protonated NMP molecules, HNMP+. Solvothermal reactions of H2BDS and MnCO3 in the solvents DMF, NMP and dimethylacetamide (DMA), respectively, yielded the disulfonates Mn(BDS)(DMF)2 (III) (P[1 with combining macron], Z = 1, a = 514.3(1) pm, b = 926.2(1) pm, c = 940.2(1) pm, α = 93.552(8)°, β = 99.993(7)°, γ = 99.237(7)°, R1; wR2 (Io > 2σ(Io)) = 0.0290; 0.0637), Mn(BDS)(DMA)2 (IV) (P[1 with combining macron], Z = 2, a = 936.00(4) pm, b = 984.94(4) pm, c = 1034.75(5) pm, α = 81.606(2)°, β = 88.941(2)°, γ = 82.364(2)°, R1; wR2 (Io > 2σ(Io)) = 0.0387; 0.1046) and Mn(BDS)(NMP)2 (V) (P[1 with combining macron], Z = 2, a = 962.97(3) pm, b = 976.76(3) pm, c = 1034.23(3) pm, α = 89.371(1)°, β = 78.839(1)°, γ = 87.604(2)°, R1; wR2 (Io > 2σ(Io)) = 0.0243; 0.0713). In the crystal structures of the three compounds, the octahedrally coordinated Mn2+ ions are linked by the disulfonate ions to layers according to 2{Mn(BDS)4/4(L)2} (L = DMF, DMA, NMP). The thermal analysis of all compounds shows that they can be desolvated completely and that the remaining solvent-free sulfonates exhibit decomposition temperatures up to 500 °C that is exceptionally high when compared to the respective carboxylates. Temperature-dependent magnetic susceptibility measurements of [NH2(CH3)2]2{Mn(B4S)(DMF)2} show paramagnetic behavior of the Mn2+ ions.

Graphical abstract: 1,2,4,5-Benzenetetrasulfonic acid and 1,4-benzenedisulfonic acid as sulfo analogues of pyromellitic and terephthalic acids for building coordination polymers of manganese

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Article information


Submitted
04 Aug 2014
Accepted
15 Oct 2014
First published
16 Oct 2014

This article is Open Access

CrystEngComm, 2014,16, 11064-11077
Article type
Paper
Author version available

1,2,4,5-Benzenetetrasulfonic acid and 1,4-benzenedisulfonic acid as sulfo analogues of pyromellitic and terephthalic acids for building coordination polymers of manganese

C. Zitzer, T. W. T. Muesmann, J. Christoffers, C. Schwickert, R. Pöttgen and M. S. Wickleder, CrystEngComm, 2014, 16, 11064
DOI: 10.1039/C4CE01618A

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